O-Alkyl-S-alkyl-S-{8 1,2-bis(alkoxycarbonyl)ethyl{9 dithiophosphates

ABSTRACT

New thiolphosphoric acid esters, their manufacture and use as pesticides is disclosed. The compounds correspond to the formula     WHEREIN R1 represents methyl or ethyl, R2 represents n-propyl, n-butyl, i-butyl, sec.butyl, R3 and R4 each represents a straight or branched alkoxy radical containing 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy or n-hexyloxy and are effective against insects and representatives of the order Acarina. D R A W I N G

United States Patent [191 Oswald et al.

111 3,887,658 June 3,1975

[ O-ALKYL-S-ALKYL-S-[l,2-

BIS( ALKOXYCARBONYL)ETHYL]DITI-IIO- PHOSPHATES [75] Inventors: Alexis A. Oswald, Mountainside;

Paul L. Valint, Woodbridge, both of [21] App]. No.: 354,404

[30] Foreign Application Priority Data Apr. 27., 1972 Switzerland 6265/72 [52] U.S. Cl. 260/942; 424/212 [51] Int. Cl C07t' 9/16; A01n 9/36 [58] Field of Search 260/942 [56] References Cited UNITED STATES PATENTS 2,578,652 12/1951 Cassaday 260/942 3,081,332 3/1963 Ailman et al.. 260/942 3,309,371 3/1967 Curry et al 260/925 FOREIGN PATENTS OR APPLICATIONS 1,001,065 8/1965 United Kingdom '260/942 Primary Examiner-Anton H. Sutto Attorney, Agent, or FirmFrederick I-l. Rabin [5 7] ABSTRACT New thiolphosphoric acid esters, their manufacture and use as pesticides is disclosed. The compounds correspond to the formula wherein R represents methyl or ethyl, R represents n-propyl, n-butyl, ibutyl, sec.butyl, R and R each represents a straight or branched alkoxy radical containing 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy or n-hexyloxy and are effective against insects and representatives of the order Acarina.

8 Claims, No Drawings 1 O-ALKYL-S-ALKYL-S-[l ,2- BIS(ALKOXYCAONYL)ETI-IYL]DITHIOPHOS- PHATES The present invention relates to thiolphosphoric acid esters, processes for their manufacture, and to their use in pest control.

The thiolphosphoric acid esters have the formula wherein R represents methyl or ethyl, R represents n-propyl, n-butyl, i-butyl, sec.butyl, R and R each rep-- resents a straight or branched alkoxy radical containing 1 to 6 carbon atoms such as methoxy, ethoxy, npropoxy, isopropoxy or n-hexyloxy.

Preferred compounds on account of their activity are those of the formula I, wherein R, represents methyl or I the following methods described e.g. in

The compounds of the formula I have a broad bio-' cidal activity spectrum and can be used for combating diverse kinds of plant and animal pests.

The compounds of the formula I possess in particular insecticidal and acaricidal properties and can be used against all development stages, e.g. eggs, larvae, pupae, nymphs, and adults of insects and representatives of the order Acarina, for example against insects of the families: Tetigonidae, Gryllidae, Gryllotalpidae, Blattidae, Peduviidae, Phyrrohocoriae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyralidae, Culcidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae a Pulicidae, also Acarida of the families Ixodidae, Argasidae, Tetranychidae a Dermanyssidae. The insecticidal and/or acaricidal action can be substantially broadened and adapted to suit the particular circumstances by the addition of other insecticides and/or acaricides.

Suitable additives include, for example, the following US. Pat. No. 2,578,652: active substances:

u 1 i -sm r. R23 \u\.L \i, out.) l

' (Ill-C("R I \ii u P-SH 1 omen? R75 (IV) (v) 3 'R o s 12--s--cn-c0a I 7 s (V I)- R10 (nu coa or HER. (r111) j (v1) or l 1, 114]. 1

or )1 OJ) In the formulae II to Xi, R to R have the meanings given for the formula I, R represents alkyl with l to 4 cai bon atoms, X represents oxygen or sulphur, Hal represents chlorine, bromine, or iodine, and M represents ammonium alkyl-ammonium with 1 to 4 carbon atoms in the alkyl moiety, or alkali metal.

In reaction I it is sometimes necessary to use catalysts, e.g. potassium iodide. Reaction 2 is initiated by using ultraviolet light, peroxides, e.g. hydrogen peroxide, or hydroquinone. Reactions 1 to 4 are carried out at a reaction temperature between 090C, in particular at 20 to C, at normal pressure and in solvents or diluents.

Examples of suitable solvents or diluents are: ethers ORGANIC PHOSPI-IORUS COMPOUNDS 0 Z-methoxycarbamyll -methylvinyldimethylphosphate (MEVINPI-IOS) Dimethyl-1-methyl-2-(methylcarbamoyl)- vinylphosphate cis MONOCROTOPI-IOS) 3-(dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (DICROTOPHOS) 2-chloro-2-diethylcarbamoyll -methylvinyldimethylphosphate (PHOSPHAMIDON) 0,0-diethyl-O(or S)-2(ethylthio)-ethylthiophosphate (DEMETON) 3 S-ethylthioethy]-0,0-dimethyl-dithiophosphate (THI- OMETON) QO-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) 0,0-diethyl-S-2-(ethylthio)ethyldithiophosphate (DI- SULFOTON) 0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETON METHYL) 0,0-dimethyl-S-( 1,2-dicarbethoxyethyldithiophosphate (MALATHION) 0,0,0,0-tetraethyl-S,S methylene-bisdithiophosphate (ETHION) O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethyl-S-(N-methyl-N- formylcarbamoylmethyl)-dithiophosphate MOTHION) 0,0-dimethyl-S-(N-methylcarbamoylmethyl)- dithiophosphate (DIMETHOATE) 0,0-dimethyl-O-p-nitrophenylthiophosphate RATHlON-METHYL) 0,0-diethyl-O-p-nitrophenylthiophosphate THION) O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN) 0,0-dimethyl-O-(4-nitro-m-tolyl)-thiophosphate (FENITROTHION) 0,0-dimethyl-O-2,4,5-trichlorophenylthiophosphate (RONNEL) O-ethyl-O-2,4,5-trichlorophenylethylthiophosphate (TRICHLORONATE) 0,0-dimethyl-O-Z,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS) 0,0-dimethyl-O-(2,5-dichloro-4-iodophenyl)- thiophosphate (JODOFENPHOS) 4-tert.butyl-2-chlorophenyl-N-methyl-O- methylamidophosphate (CRUFOMATE) 0,0-dimethyl-O-(3-methyl-4-methylmercaptophenyl)- thiophosphate (FENTHION) Isopropylamino-O-ethyl-O-(4-methylmercapto-3- methylphenyl)phosphate 0,0-diethyl-O-p(methylsulphinyl)phenylthiophosphate (FENSULFOTHION) O-p-(dimethylsulphamido)-phenyl-0,0-dimethylthiophosphate (FAMPHUR) 0,0,0',O'-tetramethyl-0,0-thiodi-p-phenylenethiophosphate O-ethyl-S-phenyl-ethyldithiophosphate 0,0-dimethyl-O-(a-methylbenzyl-3-hydroxycrotonyl)- phosphate 2-chloro-1-(2,4-dichlorophenyl)vinyldiethylphosphate (CHLORFENVINPHOS) l-chloro-1-(2,4,5-trichlorophenyl)vinyldimethylphosphate (FOR- (PARA- O-[Z-chloro-l-(2,5-dichlorophenyl)]viny1-0,0-

diethylthiophosphate Phenylglyoxylonitriloxime-0,0-dimethylthiophosphate (PHOXIM) 0,0-diethyl-O-( 3-chloro-4-methyl-2-oxo-2-H- l benzopyran-7-yl)thiophosphate (COUMAPHOS) 2,3-p-dioxandithiol-S,S-bis(0,0-diethyldithiophosphate) (DIOXATHION) 5-[( 6-chloro-2-oxo-3-benzoxazolinyl)methyl]0,0-

diethyldithiophosphate (PHOSALONE) 2-( diethoxyphosphinylimino )-l ,3-dithiolane 0,0-dimethyl-S-[ Z-methoxy- 1 ,3,4-thiadiazol-5-( 4H onyl-(4)-methyl]dithiophosphate 0,0-dimethyl-S-phthalimidomethyl-dithiophosphate (IMIDAN) 0,0-diethyl-O-( 3 ,5 ,6-trichloro-2-pyridyl )thiophosphate I 4 0,0-diethyI-O-2-pyrazinylthiophosphate ZIN) 0,0- diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)thiophosphate (DIAZINON) 0,0-diethyl-O-(2-quinoxaly1)thiophosphate 0,0-dimethyl-S-(4-oxo-1 ,2,3-benzotriazin-3( 4H ylmethyl)dithiophosphate (AZINPHOSMETHYL) 0,0-diethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)- v ylmethyl)dithiophosphate (AZINPHOSETHYL) S-[(4,6-diamino-s-triazin-2-yl)methy1]-0,0- dimethyldithiophosphate (MENAZON) 0,0-dimethyl-O-(3-chloro-4-nitrophenyl)thiophosphate (CHLORTHION) 0,0-dimethyl-O(or S')-2-(ethylthioethyl)thiophosphate (DEMETON-S-METHYL) 2-(0,0-dimethyl-phosphoryl-thiomethy1)-5-methoxypyrone-4-3,4-dichlorobenzyl-triphenylphosphoniumchloride 0,0-diethy1-S-(2,5-dichlorophenylthiomethyl)dithiophosphate (PHENKAPTON) 0,0-diethyl-O-(4-methyl-cumarinyl-7)-thiophosphate (POTASAN) 5-amino-bis(dimethylamido)phosphinyl-3-phenyl- 1,2,4-triazole (TRIAMIPHOS) N-methyl-S-(0,0-dimethylthiolphosphoryl)-3-thiavaleramide (VAMIDOTHION) 0,0-diethyl-O-[ Z-dimethylamino-4-methylpyrimidyl- (6)]-thioph0sphate (DIOCTHYL) 0,0-dimethyl-S-(methylcarbamoylmethyl)- thiophosphate (OMETHOATE) O-ethyl-O-( S-quinolinyl )-phenylthiophosphonate (OXINOTHIOPHOS) O-methyl-S-methyl-amidothiophosphate (MONITOR) O-methyl-O-(2,5-dichloro-4-bromophenyl)-benzothiophosphate (PHOSVEL) 0,0,0,0-tetrapropyldithiophosphate 3-(dimethoxyphosphinyloxy)-N-methyl-N-methoxycis-crotonamide (Tl-[IONA- 0,0-dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate (ETHOATE-METHYL) 0,0-diethyl-S-(N isopropylcarbamoylmethyl)- dithiophosphate (PROTHOATE) S-N-( 1-cyano-1-methylethyl)carbamoylmethyldiethylthiolphosphate (CYANTHOATE) S-(Z-acetamidoethyl)-0,0-dimethyldithiophosphate Hexamethylphosphoric acid triamide (HEMPA) 0,0-dimethyl-O-(2-chloro-4-nitrophenyl)thiophos phate (DICAPTHON) 0,0-dimethyl-O-p-cyanophenyl thiophosphate (CYA- NOX) O-ethyl-O-cyanophenylthiophosphonate 0,0-diethyl-O-2,4-dichlorophenylthiophosphate (DI- CHLORFENTHION) 5 O-2,4-dichlorophenyl-O-methylisopropylamidothiophosphate 0,0-diethyl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS-ETHYL) dimethyl-p-(methylthio)phenylphosphate 0,0-dimethyl-O-p-sulphamidophenylthiophosphate O-[p-(p-chlorophenyl)-azophenyl]0,0-dimethylthiophosphate (AZOTHOATE) O-ethyl-S-4-chlorophenyl-ethy1dithiophosphate O-isobutyl-S-p-chlorophenyl-cthyldithiophosphate QO-dimethy-S-p-chlorophenylthiophosphate 0,0-dimethyl-S-(p-chlorophenylthiomethyl)dithiophosphate 0,0-diethyl-p-chlorophenylmercaptomethyldithiophosphate (CARBOPHENOTHION) 0,0diethyl-S-p-chlorophenylthiomethy]- thiophosphate 0,0-dimethyl-S-(carbethoxy-phenylmethyl )dithiophosphate (PI-IENTI-IOATE) 0,0-diethyl-S-(carbofluorethoxy-phenylmethyl)- 5 dithiophosphate 0,0-dimethyl-S-carboispropoxy-phenylmethyl)- dithiophosphate 0,0-diethyl-7-hydroxy-3,4-tetramethylenecoumarinyl-thiophosphate (COUMITHOATE) 2-methoxy-4-I-I-1 ,3 ,2-benzodioxaphosphorin-2- sulphide 0,0-diethyl-O-(5-phenyl-3-isooxazolyl)thiophosphate 2-( diethoxyphosphinylimino )-4-m et hyl- 1 ,3-dithiolane tris-(Z-methyl-1-azirdinyI)-phosphine oxide (ME- TEPA) S-(2-chloro-l-phthalimid0ethyl)-0,0-diethyldithiophosphate N-hydroxynaphthalimido-diethylphosphate dimethyl-3,5,6-trichIoro-2-pyridylphosphate 0,0-dimethyI-O-(3,5,6-trichloro-2-pyridyl)thiophosphate I S-2-(ethylsulph0nyl)ethyl dimethylthiolphosphate (DIOXYDEMETON-S-METHYL) diethyl-S-2-(ethylsulphinyhethyl (OXIDISULFOTON) bis-0,0-diethylthiophosphoric acid anhydride (SUL- FOTEP) dimethyl-l ,3-di( carbomethoxy)- l -propen-2-phosphate dithiophosphate dimethyl-( 2 ,2,2-trichloro- 1 -butyroyloxyethyl )phosphate (BUTONATE) 0,0-dimethyl-O-( 2,2-dichlor0- l -methoxyvinyl)phosphate bis-dimethylamido)fluorphosphate (DIMEFOX) 3,4-dichlorobenzyl-triphenylphosphoniumchloride dimethyl-N-methoxymethylcarbamoylmethyldithiophosphate (FORMOCARBAM 0,0-diethyl-O-( 2,2-dichlorol -chloroethoxyvinyl)- phosphate 0,0-dimethyl-O-( 2,2-dichlorol -chloroethoxyvinyl phosphate O-ethyl-S,S-diphenyldithiolphosphate O-ethyl-S-benzyl-phenyldithiophosphonate 0,0-diethyl-S-benzyl-thiophosphate 0,0-dimethyl-S-(4-chlorophenylthiomethyl)dithiophosphate (METHYLCARBOPHENOTI-IION) 0,0-dimethyl-S-(ethylthiomethyl)dithiophosphate diisopropylaminofluorophosphate (MIPAFOX) 0,0-dimethyl-S-(morpholinylcarbamoylmethyl)dithiophosphate (MORPHOTI-IION) bismethylamido-phenylphosphate 0,0-dimethyl-S-( benzenesulphonyl )dithiophosphate 0,0-dimethyl-(S and O)-ethylsulphinylethylthiophosphate 0,0-diethyl-O-4-nitrophenylphosphate triethoxy-isopropoxy-bis( thiophosphiny] )disulphide 2-methoxy-4I-I-1,3,2-benzodioxaphosphorin-Z-oxide octamethylpyrophosphoramide (SCHRADAN) bis-(dimethoxythiophosphyinylsulphido)- phenylmethane- N,N,N',N'-tetramethyldiamidoflurorphosphate (DIMEFOX) O-phenyl-O-p-nitrophenyl-Methanethiophosphonate (COLEP) O-methyl-O-(2-chloro-4-tert.butyl-phenyl)-N- methylamidothiophosphate (NARLENE) O-ethyI-O-( 2,4-dichlorophenyl )-phenylthiophosphonate 0,0-diethyl-O-( 4-methylme rcapto-3 ,5

dimethylphenyl)'thi0phosphate 4,4'-bis -(0,0-dimethylthiophosphoryloxy)-diphenyl disulphide 0,0-di-(,8-chlor0ethyl )-O-( 3-chloro-4-methylcoumarinyl-7 )-phosphate S-( l-phthalimidoethyl)-0,0-diethyldithiophosphate 0,0-dimethyl-O-( 3-chloro-4-diethylsulphamylphenyl thiophosphate O-methyl-O-(2-carbisopropoxyphenyl)-amidothi0- phosphate 5- 0,0-dimethylphoshporyl)-6-chloro-bicyclo( 3 2.0

heptadiene( 1,5) O-methyl-O-(Z-i-propoxycarbonyl-1-methylvinyl)- ethylamidothiophosphate.

NITROPI-IENOLS AND DERIVATIVES 4,6-dinitro-6-methylphenol, sodium salt [Dinitrocresol] dinitrobutylphenol-(2,2,2")-triethanolamine salt 2-cyclohexyl-4,6-dinitrophenyl [Dinex] 2-1-methylheptyl)-4,6-dinitrophenyl-crotonate [Dinop] 2-sec.butyl-4,6-dinitrophenyl-3-methyl-butenoate [Binapacryl] 2-sec.butyl-4,6-dinitrophenyl-cyclopropionate 2-sec.butyl-4,6-dinitrophenylisopropylcarbonate [Dinobuton] MISCELLANEOUS pyrethrin I pyrethrin II 3-allyl-2-methyl-4-oxo-2-cyclopentanl -ylcrysanthemumate (Allethrin) 6-chloropiperonyl-ch rysanthemumate (Barthrin) 2,4-dimethylbenzyl-chrysanthemumate (Dimethrin) 2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate 4-chlorobenzyl-4-ch]orophenylsulphide sid] 6-methyl-2-oxo- 1 ,3-dithio1o-[ 4,5-b -quinoxaline (Quinomethionate) (I)-3-(2-furfuryl)-2-methyl-4-oxocyclopent-2-enyl(I)- (cis+trans)-chrysanthemum-monocarboxylate [Furethrin] 2-pivaloyl-indane-l ,3-dione [Pindon] 4-ehIorobenzyl-4-fluorophenyl-sulphide side] 5 ,6-dichloro-1-phenoxycarbamyl-2-trifluoromethylbenzimidazole [Fenozaflor] p-chlorophenyl-p-chlorobenzenesulphonate [Ovex] p-chlorophenyI-benzenesulphonate [Fenson] p-chl0rophenyl-2,4,5-trichlorophenylsulphone radifon] p-chlorophenyl-2,4,5-trichlorophenylsulphide sul] p-chlorobenzyl-p-chloropheny]sulphide side] 2-thiol ,3-dithiolo-(5,6)-quinoxaline [Thiochinox] prop-2-yny1-(4-t-butylphenoxy)-cyclohexylsulphite [Propargil [Chloroben- [F luoroben- [Tet- [Tetra- [Chloroben- FORMAMIDINES l-dimethyl-2-(2-methyl-4-chlorophenyl)- formamidine (CHLORODIMEFORM) 9 l,3-bis( carbamoylthio) 2-(N,N-dimethylamino)- propanehydrochloride ,5-dimethylhydroresorcinoldimethylcarbamate 2-[ethyl-proparglyamino]-phenyl-N-methylcarbamate 2[ methyl-propargylamino]-phenyl-N- methylcarbamate 4-[dipropargylamino]-3-tolyl-N-methylcarbamate 4-[dipropargylamino]-3 ,5-xylyl-N-methylcarbamate 2-[-allyl-isopropylamino ]-phenyl-N-methylcarbamate 3-[allyl-isopropylamino]-phenyl-N-methylcarbamate CHLORINATED HYDROCARBONS 'y-hexachlorocyclohexane [GAMMEXANE; LINDAN;

y HCH] l,2,4,5 ,6,7 ,8,8-octachloro-3a,4,7,7a-tetrahydro-4,7-

methylene indane [CHLORDAN] 1,4,5 ,6,7,8 ,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-

methylene indane [HEPTACHLOR] 1,2,3 ,4,10, lO-hexachloro-l ,4,4a,5,8,8a-hexahydroendol ,4-exo-5,8-dimethanonaphthalene [ALDRIN] 1,2,3 ,4, 1 O, 1 O-hexachloro-6,7-epoxy-l ,4,a,5,6,7,8,8a-

octahydro-exo-1,4-endo-5 ,8-dimethanonaphthalene.

[DlFLORlN] 1,2,3.4,l0,lO-hexachloro-5,7-epoxy-l,4,4a,5,6,7,8,8a-

octahydro-endo-endo-S,S-dimethanonaphthalene [ENDRIN] The compounds of the formula I may be used as pure active substance or together with suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technique such, for example, as solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions, or suspensions, in the conventional formulation which is commonly employed in application technology. Mention may also be made of cattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may take, and be used in, the following forms:

Solid forms:

Dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules. Liquid forms:

a. active substances which are dispersible in water:

wettable powders, pasts, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay,

dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materi-- als, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used singly or in admixture with one another.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, S10 granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/liter to 600 g/liter can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.

It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product.

To these mixtures can also be added additives which stabilise the active substance and/or non-ionic, anionic and cationic surface active substances, which, for example, improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface-active substance and anti-foam agents and, optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Suitable carriers are, for example, those mentioned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulphonic acid, in addition, alkylaryl sulphonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols, heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salts of oleoyl methyl tauride, ditertiary acetylene glycols, dialkyl dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are mixed, ground, sieved and strained with the additives cited hereinabove, in such a manner that, the size of the solid particles does not exceed 0.02 to 0.04 ,u. in wettable powders, and 0.03 p. in pastes. To produce emulsifiable concentrates and pastes, dispersing agents such as those cited above, organic solvents, and water are used. Examples of suitable solvents are: alcohols, benzene, xylene, toluene, dimethyl sulphoxide, and mineral oil fractions which boil between 120 and 350C. The solvents must be practically odourless, not phytotoxic, and inert to the active substances.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substances, or several active substances of the general formula 1, are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils, singly or in admixture with each other, can be used as organic solvents.

The content of active substance in the above described agents is between 0.1 to 95%, in which connection it should be mentioned that, in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.

The active substances of the formula I can, for example, be formulated as follows:

DUSTS The following substances are used to manaufacture (a) a 5% and (b) a 2% dust:

a. 5 parts of active substance 95 parts of talcum 2 parts of active substance 1 part of highly disperse silicic acid 97 parts of talcum.

The active substances are mixed with the carriers and ground.

GRANULES The following substances are used to produce 5% granules: w

5 parts of active substance,

025 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The

thus obtained solution is sprayed on kaolin, and the acetone subsequently evaporated in vacuo.

WETTABLE POWDER The following constituents are used for the preparation of (a) a 40%, (b) and (c) a 25%, and (d) a 10% wettable powder:

a. 40 parts of active substance,

5 parts of sodium lignin sulphonate,

1 part of sodium dibutyl-naphthalene sulphonate,

54 parts of silicic acid.

25 parts of active substance,

4.5 parts of calcium lignin sulphonate,

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl naphthalene sulphonate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalk,

28.1 parts of kaolin.

25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol,

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

8.3 parts of sodium aluminium silicate,

16.5 parts of kieselguhr,

46 parts of kaolin.

10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.

EMULSIFIABLE CONCENTRATES 10 parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture, 5 parts of dimethylformamide,

57.5 parts of xylene. I From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.

3 ,8 8 7,65 8 13 14 SPRAY 26.6 g of potassium O-ethyl-S-sec. amylf n t d t dithiophosphate and 2 g of potassium iodide are given T e o owmg P 1 are use 0 prepare a 5% to 200 ml of acetonitrile. Then 25.3 of bromosuccinic g g of active Substance, acid diethyl ester are added and the mixture is stirred 1 part of epichlomhydrin, 5 overnight at room temperature and subsequently for 6 94 parts of benzine (boiling limits c hours at 5060C. After the batch has cooled, the salts are filtered off with suction, the solution is evaporated EXAMPLE I in vacuo, and the residue is taken up in methylene chloride. The solution is washed successively with 50 ml of water, 50 ml of normal sodium hydroxide solution, and 50 ml of water, and the solvent is removed in vacuo at 50C bath temperature, to leave as residue the active 0 n O u substance of the above described formula as a yellow 2 5 H oil with the refractive index n 1.4833. Yield: 31.6 g. (sec )G H S I I The following compounds are also obtained in analogous manner.

Manufacture of the compound of the formula 10 EXAMPLE 2 A. Insecticidal ingest poison action Tobacco and potato plants were sprayed with a 0.05% aqueous active substance emulsion (obtained from a 10% emulsifiable concentrate.

After the coating had dried, the tobacco plants were populated with Spodoptera littoralis caterpillers in the L stage and Heliothis virescens caterpillers in the L stage and the potato plants with Colorado beetle larvae (Leptinotarsa decemlineata). The test was carried out at 24C and 60% relative humidity. In the above test, the compounds according to Example I displayed good ingest poison action against Spodoptera litroralis, Heliot/u's rirescens and Leptinotursa decemlineala.

B. Insecticidal contact action Rooted bean plants (vicia faba) reared in pots were infected one day before the application with about 200 leaf-lice (Aphisfabue) per plant. The application to the leaves populated with the lice was carried out with a pressure spray using a spray broth in a concentration of 1000 ppm (manufactured from a 25% wettable powder). Evaluation took place 24 hours after the application. In the above test the compounds according to Example l displayed good contact action against Aphis fabae.

EXAMPLE 3 Action against Chilo suppressalis Six rice plants at a time of the variety Caloro were transplanted in plastic pots (diameter at the top 17 cm) and reared to a height of about 60 cm. Infestation which Chilo suppressalis larvae (L 3-4 mm in length) took place 2 days after the active substance had been applied in granule form to the paddy water (rate of application: 8 kg of active substance per hectare). Evaluation of the insecticidal action ensued 10 days after application of the granules.

In the above test, the compounds according to Example I acted against Chilo suppressalis.

EXAMPLE 4 Action against ticks A. Rhipicephalus bursa Five adult ticks or 50 tick larvae were counted into a test tube and immersed for l to 2 minutes in 2 ml of an aqueous emulsion series each containing 100, 10, l and 0.1 ppm of test substance. The tube was then sealed with a standardised cotton wool plug and stood on its head so as to enable the cotton wool to absorb the active substance emulsion.

In the case of the adults evaluation took place after.

16 used in Test A. (The resistance refers to the tolerability of diazinon). In these tests, the compounds according to Rhipicephalus I acted against adults and larvae, of Ripicephalus bursa and sensitive and OP-resistant larvae of Boophilus microplus.

EXAMPLE 5 Action against spider mites Phaseolus vulgaris (plants) were overlaid with an in fested piece of leaf from a mass culture of Telranychus urticae 12 hours before the test for acaricidal action.

The mobile stages which had spread over the plants were sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth did not run off. The number of living and dead larvae. adults and eggs were evaluated after 2 to 7 days under a stereoscopic microscope and the result was expressed in percentages. During the interim, the treated plants were kept in greenhouse compartments at 25C.

In the above test, the compounds according to Example I acted against adults larvae and eggs of Tetranychus urticae.

We claim:

I. A thiol phosphoric acid ester of the formula wherein R represents methyl or ethyl, R represents n-propyl, n-butyl, i-butyl, sec.butyl and R and R each represents straight or branched alkoxy containing 1 to 6 carbon atoms.

2. A compound according to claim 1, wherein R represents n-propyl.

3. A compound according to claim 1, wherein R and R each is selected from the group consisting of methoxy', ethoxy, n-propoxy, isopropoxy and n-hexyloxy.

4. A compound according to claim 2, wherein R and R each is methoxy, ethoxy or isopropoxy.

- 5. O-ethyl-S-n-propyl-S-[1,2-bis-(methoxycarbonyl)- ethyl]dithiophosphate according to claim 4.

6. O-ethyl-S-n-propyl-S-[ l ,2-bis-(ethoxycarbonyl)- ethyl]-dithiophosphate according to claim 4.

7. O-ethyl-S-n-propyl-S-[ 1,2-bis- (isopropoxycarbonyl )-ethyl]-dithiophosphate according to claim 4.

8. O-methyl-S-n-propyl-S-[ l,2-bis(ethoxycarbonyl)- ethyl]-dithiophosphate according to claim 4. 

1. A thiol phosphoric acid ester of the formula
 1. A THIOL PHOSPHORIC ACID ESTER OF THE FORMULA
 2. A compound according to claim 1, wherein R2 represents n-propyl.
 3. A compound according to claim 1, wherein R3 and R4 each is selected from the group consisting of methoxy, ethoxy, n-propoxy, isopropoxy and n-hexyloxy.
 4. A compound according to claim 2, wherein R3 and R4 each is methoxy, ethoxy or isopropoxy.
 5. O-ethyl-S-n-propyl-S-(1,2-bis-(methoxycarbonyl)-ethyl)dithiophosphate according to claim
 4. 6. O-ethyl-S-n-propyl-S-(1,2-bis-(ethoxycarbonyl)-ethyl)-dithiophosphate according to claim
 4. 7. O-ethyl-S-n-propyl-S-(1,2-bis-(isopropoxycarbonyl)-ethyl)-dithiophosphate according to claim
 4. 